U.S. patent application number 14/235285 was filed with the patent office on 2014-06-05 for homoleptic rare earth triaryl complexes.
This patent application is currently assigned to ROCKWOOD LITHIUM GMBH. The applicant listed for this patent is Jorg Sundermeyer, Oliver Thomas. Invention is credited to Jorg Sundermeyer, Oliver Thomas.
Application Number | 20140155562 14/235285 |
Document ID | / |
Family ID | 46724314 |
Filed Date | 2014-06-05 |
United States Patent
Application |
20140155562 |
Kind Code |
A1 |
Thomas; Oliver ; et
al. |
June 5, 2014 |
HOMOLEPTIC RARE EARTH TRIARYL COMPLEXES
Abstract
The invention relates to chelate-stabilized homleptic triaryl
compounds based on phenylphosphoranes, to methods for preparing
same and to the use thereof as catalysts. According to the
invention, the object is achieved by homleptic rare earth triaryl
complexes of the general formula (I), where SE=Sc, Y, La, Ce, Pr,
Nd, Pm, Sm, Eu, Gd, Tb, Dy, Ho, Er, Tm, Yb or Lu; X=O, CRR';
R.sup.1, R.sup.2=phenyl; R, R'=mutually independently H, alkyl with
n=10 C atoms, phenyl or trimethylsilyl.
Inventors: |
Thomas; Oliver; (Marburg,
DE) ; Sundermeyer; Jorg; (Marburg, DE) |
|
Applicant: |
Name |
City |
State |
Country |
Type |
Thomas; Oliver
Sundermeyer; Jorg |
Marburg
Marburg |
|
DE
DE |
|
|
Assignee: |
ROCKWOOD LITHIUM GMBH
Frankfurt a. M.
DE
|
Family ID: |
46724314 |
Appl. No.: |
14/235285 |
Filed: |
August 2, 2012 |
PCT Filed: |
August 2, 2012 |
PCT NO: |
PCT/EP2012/003293 |
371 Date: |
January 27, 2014 |
Current U.S.
Class: |
526/170 ;
528/356; 534/15 |
Current CPC
Class: |
C08F 4/545 20130101;
C08F 136/08 20130101; C08G 69/14 20130101; C07F 9/5352 20130101;
C08F 4/52 20130101; C08G 63/00 20130101; C07F 9/5345 20130101; C08F
36/08 20130101; C08F 36/08 20130101; C08G 63/823 20130101; C08G
69/00 20130101; C08G 63/84 20130101; C08F 4/545 20130101 |
Class at
Publication: |
526/170 ; 534/15;
528/356 |
International
Class: |
C07F 9/53 20060101
C07F009/53; C08F 136/08 20060101 C08F136/08; C07F 9/535 20060101
C07F009/535; C08G 63/84 20060101 C08G063/84 |
Foreign Application Data
Date |
Code |
Application Number |
Aug 2, 2011 |
DE |
10 2011 080 285.1 |
Claims
1-16. (canceled)
17. A homoleptic rare earth triaryl complex of formula 1
##STR00011## wherein RE=Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,
Dy, Ho, Er, Tm, Yb or Lu; X=O, CRR; R.sup.1,R.sup.2=phenyl; R,
R'=independently of each other, H, alkyl with n=1-10 carbon atoms,
phenyl or trimethylsilyl.
18. A homoleptic rare earth triaryl complex according to claim 17,
wherein if X=O, SE=Sc, Y, Lu or Yb.
19. A homoleptic rare earth triaryl complex according to claim 17,
wherein if X=CH.sub.2, RE=Sc, Y, Lu, Sm, Gd or Dy.
20. A homoleptic rare earth triaryl complex according to claim 17
selected from the group consisting of:
[o-Sc(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3],
[o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3],
[o-Lu(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3],
[o-Yb(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3],
[o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3],
[o-SC(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3],
[o-LU(C.sub.6H.sub.4(C.sub.6H .sub.5).sub.2P=CH.sub.2).sub.3],
[o-Dy(C.sub.6 H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3],
[o-Gd(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3], and
[o-Sm(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3].
21. A method according of preparing a homoleptic rare earth triaryl
complex according to claim 17, wherein a triphenylphosphorane is
reacted with a solvated rare earth metal halogenide or solvatized
organo rare earth metal complex in the temperature range of
-30.degree. C. to 120.degree. C.
22. The method according to claim 21, wherein the reaction is
achieved by at least one of a salt elimination or hydrogen
elimination.
23. The method according to claim 21, wherein the reaction is
performed in situ as a one-pot reaction.
24. The method according to claim 21, wherein the reaction is
performed in aromatics, cyclic ethers or in mixtures from these
solvents.
25. The method according to claim 21, wherein the reaction is
performed in a temperature range between 0.degree. C. and
60.degree. C.
26. The method according to claim 21, wherein the
triphenylphosphorane is reacted with a solvatized rare earth metal
halogenide or solvatized organo rare earth metal complex at a molar
ratio of 3:1.
27. The method according to claim 22, the reaction is a salt
elimination and a lithium base is added in an equimolar amount to
the triphenylphosphorane.
28. A method of performing an organic reaction wherein the
homoleptic rare earth triaryl complex of claim 17 is present as a
reagent or catalyst for the organic reaction.
29. A method according to claim 28, wherein the homoleptic rare
earth triaryl complex is present as a catalyst for an ring-opening
polymerization in the production of polyester.
30. A method according to claim 21, wherein the homoleptic rare
earth triaryl complex is present as a precatalyst for the
polymerization of an olefin.
31. A method according to claim 30, wherein the olefin is
conjugated.
Description
[0001] The present invention relates to chelate-stabilized
homoleptic triaryl compounds based on phenylphosphoranes and to
methods for preparing same and to the use thereof as catalysts.
[0002] Compounds of the cyclometalated triphenylphosphinoxide
ligands (TPPO, according to FIG. 1) are scarce in the
literature.
##STR00001##
[0003] Weichmann et al. published compounds of this ligand in form
of a series of Sn(IV) complexes with a Lewis-azide main group
element (Abicht, H. P.; Weichmann, H., Z. Chem. 1988, 28, (2),
69-70). In addition, it was possible to provide a structural
characterization of [Sn(TPPO)Me.sub.2Cl] for the first time.
##STR00002##
[0004] Further compounds of the [M(TPPO)L.sub.n] type could be
obtained with [MnBz(CO).sub.5], eliminating toluene, and an
equivalent CO. The compound [Mn(TPPO)(CO).sub.4] also underwent
crystallographical analysis (Depree, G. J.; Childerhouse, N. D.;
Nicholson, B. K., J. Organomet. Chem. 1997, 533, (1-2), 143-151).
The first homoleptic compound was produced by reacting HgCl.sub.2
with LiC.sub.6H.sub.4PPh.sub.2 followed by oxidation of the anionic
phosphine ligand with aqueous H.sub.2O.sub.2--the [Hg(TPPO).sub.2]
also underwent structural characterization. A further compound of a
late transitional metal was synthetized in a similar fashion. The
oxidation of [o-Pt(C.sub.6H.sub.4PPh.sub.2).sub.2] with elemental
bromine yielded inter alia [Pt(TPPO).sub.2Br.sub.2] (Bennett, M.
A.; Bhargava, S. K.; Ke, M.; Willis, A. C., J. Chem. Soc, Dalton
Trans. 2000, 3537-3545).
##STR00003##
[0005] Tilley et al. were first in successfully inserting the TPPO
ligand into a rare earth metal. Due to the sterically enormously
demanding pentamethylcyclopentadienyl ligands, it was possible to
obtain [Cp*.sub.2Sm(TPPO)] as a molecularly stable compound. The
preparation was achieved either starting from
[Cp*.sub.2SmSiH.sub.3(0=PPh3)] at elevated temperatures or by the
elimination of hydrogen from [Cp*.sub.2SmO(.mu.-H)].sub.2 and two
equivalents triphenylphosphine oxide. The characterization was done
exclusively by NMR spectroscopy (Castillo, I.; Tilley, T. D.,
Organometallics 2000, 19, (23), 4733-4739).
##STR00004##
[0006] The reaction of phosphorane A with tert-butyllithium in
THF-d.sub.8 at -78.degree. C. yields only the ortho-metalated
product, as could be documented by NMR-spectroscopic analysis.
##STR00005##
[0007] The metalated compounds B only have very minimal thermal
stability at temperatures above -15.degree. C., after which point
they quickly degrade to compound C, due to the intramolecular
addition of the singlet carbene B' to a neighboring phenyl ring and
subsequent elimination of benzene (Schaub, B.; Schlosser, M.,
Tetrahedron Lett. 1985, 26, (13), 1623-1626).
##STR00006##
[0008] Rare earth metals have only in few cases been combined with
the anionic TPPM ligand. Stabilizing these compounds could always
be achieved by cyclopentadienyl ligands or the permethylated
derivatives thereof. The first representative thereof was published
as compound D in 1984 by WATSON (Watson, P. L., J. Chem. Soc, Chem.
Commun. 1983, (6), 276-277). Shortly thereafter, compound E
followed as the result of works by SCHUMANN et al. (Schumann, H.;
Reier, F. W., J. Organomet. Chem. 1984, 269, (1), 21-27). With
complex F in 1993, a compound of this class was obtained for the
first time that was also structurally characterized, (Booij, M.;
Deelman, B. J.; Duchateau, R.; Postma, D. S.; Meetsma, A.; Teuben,
J. H., Organometallics 1993, 12, (9), 3531-3540).
##STR00007##
[0009] Therefore, it is the object of the present invention to
describe novel homoleptic rare earth triaryl complexes, processes
for preparing such complex compounds and for testing the properties
thereof.
[0010] This object is achieved according to the invention by
homoleptic rare earth triaryl complexes of the general formula
1.
##STR00008##
[0011] Note: It is better not to write an indicated double bond
between P and X=CH2, because at the moment that CH2 coordinates
according to the invention, the octet on the C atom is exceeded in
case that there still is an indicated double bond. Two single
bonds, as in modified FIG. 1), are equally applicable for both
target groups (O as well as CH2).
[0012] Wherein [0013] RE=Sc, Y, La, Ce, Pr, Nd, Pm, Sm, Eu, Gd, Tb,
Dy, Ho, Er, Tm, Yb or Lu; [0014] X=O, CRR; [0015] R.sup.1,
R.sup.2=phenyl; [0016] R, R=independently of each other, H, alkyl
with n=1 [0017] bis 10 carbon atoms, phenyl or trimethylsilyl.
[0018] Preferably, if X=O, RE=Sc, Y, Lu or Yb in the homoleptic
rare earth triaryl complex. If X=CH.sub.2, RE=Sc, Y, Lu, Sm, Gd or
Dy.
[0019] The homoleptic rare earth triaryl complex according to the
invention is selected particularly preferably from the group
consisting of: [0020]
[o-Sc(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3],
[o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3],
[o-Lu(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3], [0021]
[o-Yb(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3],
[o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3], [0022]
[o-Sc(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3],
[o-Lu(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3],
[0023]
[o-Dy(C.sub.5H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3],
[o-Gd(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3],
[0024] [o-Sm(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2)3].
[0025] The homoleptic rare earth triaryl complexes according to the
invention are produced in that a triphenylphosphorane is reacted
with a solvated rare earth metal halogenide or solvated organo rare
earth metal complex in the temperature range of -30.degree. C. to
120.degree. C. The reaction occurs as a salt and/or hydrocarbon
elimination. Advantageously, the process is carried out in situ by
way of a one-pot- reaction. The conversion is achieved in
aromatics, cyclic ethers or mixtures of these solvents.
[0026] The synthesis of homoleptic compounds is achieved by
eliminating salt from the rare earth metal halogenide and three
equivalents of the lithium salt (see FIG. I). A further possibility
for preparing the same envisions eliminating hydrocarbon from the
homoleptic organo metal precursors [SER.sub.3(solv).sub.n] and
three equivalents of the phosphorane (see FIG. II). Especially
preferred is the one-pot method III (figure) that starts from the
metal halogenide and three equivalents of the phosphorane. The
deprotonation of the ortho-position is achieved in situ by adding a
stoichiometrical quantity of a lithium base RLi (R=Me,
CH.sub.2SiMe.sub.3, Bu, particularly: Ph).
##STR00009##
[0027] The described processes I-III therefore give access to a
novel class of homoleptic chelate-stabilized phenylphosphorane
complexes of rare earths. It was possible to obtain the trivalent
cations of the metals samarium, gadolinium, dysprosium, yttrium,
ytterbium, lutetium and scandium with triphenylphosporanes, such as
triphenylphosphine oxide or triphenylmethylidene phosphorane.
[0028] It is particularly preferred to run the conversion in the
temperature range of 0.degree. C. to 60.degree. C. The
triphenylphosphorane is reacted with a solvated rare earth metal
halogenide or solvated organo rare earth metal complex at a molar
ratio of 3:1.
[0029] When the reaction occurs in form of a salt elimination, it
is advantageous to add a quantity of a lithium base that is
equimolar to the used triphenylphosphorane.
[0030] The homoleptic rare earth triaryl complexes are used as
reagent or catalyst in organic reactions, as catalyst in
ring-opening polymerizations in polyester production.
[0031] The homoleptic rare earth triaryl complexes are preferably
also used as a precatalyst in the polymerization of olefins,
particularly as a precatalyst in the polymerization of conjugated
olefins.
[0032] After a first screening, the compounds show catalytic
activity in the ring-opening polymerization of
.epsilon.-caprolactone as well as, after the activation, in the
diene polymerization of isoprene. With TLC measurements and
NMR-spectroscopic analyses it was possible to document a high
fraction of naturally-identical 1,4-cis-polyisoprene in the
polymer.
[0033] The invention will be described in further detail below
based on the embodiments that are provided for illustration.
[0034] Insofar as substances were used that react sensitively to
water or oxygen, the SCHLENK technique was applied. The used glass
instruments were heated in a high vacuum and filled with argon 4.8
by AIR LIQUIDE after cool-down. The argon that was used for this
purpose was dried using a column that was filled with
P.sub.4O.sub.10 granules and then with Solvona.RTM.. Weigh-ins and
sample preparations for analytical studies, as well as the storage
of oxygen- and/or hydrolysis-sensitive substances were done in
glove boxes (Type MB 150 BG-I, BRAUN, Lab Master 130, by the BRAUN
company) and under a nitrogen atmosphere. The used solvent, if
needed, was dried and purified according to standard methods under
a protective gas atmosphere..sup.2 The solvents were dehydrated,
following pre-drying and destillation, in absorption columns over
aluminum oxide/molecular sieve 3A/R3-11G catalyst (BASF).
[0035] Unless indicated otherwise, commercially available feed
materials were purchased from the companies ACROS ORGANICS,
SIGMA-ALDRICH And MERCK. Any purification that may have been
carried out prior to using these substances is described in the
associated synthesis protocols.
[0036] NMR Spectroscopy
[0037] The NMR spectra were recorded on these instruments: BRUKER
Avance 300 (.sup.1H(300.1 MHz), .sup.13C(75.5 MHz), .sup.31P(121.5
MHz), .sup.19F(282.4 MHz)), BRUKER DRX 400 (.sup.1H(400.0 MHz),
.sup.13C(100.6 MHz), .sup.31P(161.9MHZ), .sup.11B(128.4 MHZ)),
BRUKER DRX 500 (.sup.1H(500.1 MHz), .sup.13C(125.8 MHz),
.sup.31P(202.3 MHz)). All spectra were .sup.1H-decoupled and,
unless indicated otherwise, recorded at 298 K. The information as
to the chemical shift .delta. was provided in ppm relative to a
corresponding standard (.sup.1H & .sup.13C: TMS, .sup.31P: 85%
H.sub.3PO.sub.4, .sup.19F: CFCl.sub.3, .sup.11B: 15% solution of
[BF.sub.3Et.sub.2O] in CDCl.sub.3). The coupling constant
.sup.nJ.sub.AB describes the coupling of two nuclei A and B with
1/2 nucleic spin over n bonds. The .sup.31P-NMR spectra were
calibrated relative 85% phosphoric acid as internal standard. The
calibration of the .sup.1H and .sup.13C spectra was done by
residual proton and solvent signals of the corresponding
dedeuterized solvent (.sup.1H/.sup.13C:C.sub.6D.sub.6 (7.16/128.02
ppm), THF-d.sub.8 (3.58/67.40 ppm), toluene-d.sub.8: (2.08/20.5
ppm). The multiplicity of the signals is indicated by: s=singlet;
d=doublet; dd=doublet of doublet; t=triplet; dt=doublet of triplet;
q=quadruplet; quin=quintet; sept=septet, m=multiplet; br=wide
signal. In the analysis of the NMR spectra, the nomenclature for
the position was selected as shown below in FIG. 9 on the
twice-substituted phenyl ring.
##STR00010##
[0038] The content of the elements C, H and N was established with
the instrument CHN-Rapid by HERAEUS. Samples of water- and
air-sensitive substances were filled inside the glove box in
cold-welded zinc crucibles. The chloride content was established
argentometrically. The information is provided in weight-percent,
as in the elemental analysis.
[0039] Analysis of the Crystalline Structure
[0040] The monocrystal x-ray diffractograms were taken on surface
area detector systems (IPDS I, IPDS II by STOE) at the Department
of Chemistry of the Philipps-University of Marburg by Dr. K. Harms,
G. Geisseler and R. Riedel. A standard graphite monochromator
(Mo-Ka-radiation, .lamda.=71.073 pm) was employed. The data were
gathered with IPDS Software X-Area by the company STOE. The
collected data were integrated in the service department, while we
did the dissolution and purification steps ourselves. Absorption
corrections were done semi-empirically, insofar as possible, using
multi-scans. Direct methods were used for the structural solution
(Sir-92, Sir-97, Sir-2002, Sir-2004 and SHELXS-86). To refine
results, the method of the smallest error square was employed
(SHELXL-97). With the exception of the hydrogen atoms, the
positions of all atoms were anisotropically refined. Hydrogen atoms
that are involved in the structural formation of hydrogen bridge
formations or whose presence has a determinative influence on the
molecular structure, were localized in the difference Fourier map
and isotropically refined. The Diamond program was used for
preparing the structures. The results of the crystal structure
analyses are compiled in the crystallographic annex.
[0041] Infrared Spectroscopy
[0042] The IR spectra were recorded on an ATR-FT-IR spectrometer of
the Alpha-P type BRUKER. The measurements were taken inside the
glove box in substance. The absorption bands are indicated in
cm.sup.-1. The absorption band characteristics are described as
follows: w=weak, m=medium, s=strong, br=broad, v=reciprocal
wavelength in cm.sup.-1.
[0043] Mass Spectrometry
[0044] Mass spectra of the electron impact (EI) and field
desorption (FD) were recorded with the spectrometer FINNIGAN MAT
CH7 (electron energy=70 eV). Air- and/or hydrolysis-sensitive
samples were prepared inside the glove box. The indicated m/z
values relate to the isotopes with the greatest natural frequency
by which they are encountered. The most important fragments are
noted.
[0045] Gel Permeation Chromatography (GPC)
[0046] Molecular weights and polydispersities were established by
gel permeation chromatography relative to polystryrol standards in
THF at 20.degree. C. The GPC measurement of the polyisoprene was
taken in pure THF, while 5% trifluoroascetic acid (v/v) was added
to THF as eluent for the measurement of the polyesters.
[0047] Thermogravimetric Analysis (TGA) & Differential Scanning
Calorimetric Analysis (DSC)
[0048] The thermogravimetric analysis was done on a TGA/SDTA 851
instrument (by METTER TOLEDO). For the TGA measurements, the sample
was weighed in into a 70 .rho.L aluminum oxide crucible, each time
with the ultra-micro scale integrated in the instrument. The DSC
measurements of the polymer samples were taken with a DSC 821
instrument by METTER TOLEDO. To this end, 6 to 8 mg of the
substance were weighed in each time in a 40 .mu.L aluminum
crucible. The lid of the sealed crucible was pierced with a hole to
ensure equalization of pressure. The used temperature program had
two cycles. The samples were measured inside a temperature range of
-90 to 60.degree. C. with heating rates of 10 K/min.
EXAMPLE 1
[0049] [o-Sc(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3]. 184
mg [ScCl.sub.3(thf).sub.3] (0.5 mmol) was weighed in together with
418 mg triphenylphosphine oxide (1.5 mmol) to which is added 10 mL
THP. The suspension was stirred for
[0050] 30 minutes at room temperature. No formation of a coarse
flaky solid occurred.
[0051] The substance was then cooled to 0.degree. C., 0.75 mL of a
PhLi solution (20% solution in Bu.sub.2O, 1.5 mmol) was added, and
stirring was continued for another two hours at the given
temperature. The suspension slowly turned a brown color, wherein
the major part of the solid material became dissolved. The solvent
was removed completely, and the obtained brown solid was taken up
in benzene and filtered with Chelite.RTM.. The benzene was removed
in a fine vacuum, and the product was recrystallized from THP at
-30.degree. C. After decanting, the substance was dried in a fine
vacuum. 118 mg (27%) of a beige-brown-colored solid material was
obtained.
[0052] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): .delta.=6.83-7.06
(m, 8H, H.sub.0, H.sub.p, H.sub.2, H.sub.4), 7.67-7.74 (m, 5H,
H.sub.m, H.sub.3), 8.24 (d, 1H .sup.3J.sub.HH=6.99 Hz, H.sub.5)
ppm
[0053] .sup.13C-NMR (75.5 MHz, C.sub.6D.sub.6): .delta.=124.5 (d,
.sup.3J.sub.CP=14.4 Hz, C.sub.3), 128.3 (d, .sup.2J.sub.CP=12.1 Hz,
Co), 129.2 (d, .sup.4J.sub.CP=4.0 Hz, C.sub.4), 131.4 (d,
.sup.4J.sub.CP=2.4 Hz, C.sub.p), 132.7 (d, .sup.3J.sub.CP=10.4 Hz,
C.sub.m), 133.2 (d, .sup.1J.sub.CP=97.7 Hz, C.sub.ipso), 140.2 (d,
.sup.3J.sub.CP=24.8 Hz, C.sub.5), 139.7 (d, .sup.1J.sub.CP=119.5
Hz, C.sub.1), (C.sub.Sc could not be observed) ppm.
[0054] .sup.31P-NMR (121.5 MHz, C.sub.6D.sub.6): 5=43.4 ppm
[0055] Elemental analysis C.sub.54H.sub.42O.sub.3P.sub.3Y (876.79
g/mol); calculated C, 73.97; H, 4.83; N, 0.0; found: C, 72.54; H,
5.37; N, 0.0
[0056] IR spectroscopy (v/cm.sup.-1): 3011(br), 1483(w), 1436(s),
1415(w), 1222(w), 1195(w), 1131(s), 1119(s), 1079(s), 1063(s),
1025(m), 998(m), 748(w), 721 (s), 692(s), 628(s), 537(s), 463(s),
443(s), 414(s)
EXAMPLE 2
[0057] [o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3]. 410 mg
[YCl.sub.3(thf).sub.3] (1.0 mmol) was weighed in together with 835
mg triphenylphosphine oxide (3.0 mmol) to which was added 15 mL
THP. The suspension was stirred for 30 min at RT during which time
the fine crystalline substances turned into a coarse flaky solid
material. The substance was then cooled to 0.degree. C., 1.5 mL of
a PhLi solution (20% solution in Bu.sub.2O, 3.0 mmol) was added,
and the substance was stirred for two more hours at the given
temperature. The suspension increasingly turned a brown color,
wherein the solid material became dissolved for the most part. The
solvent was then removed completely and the obtained brown solid
material was taken up in benzene and filtered with Chelite.RTM..
The filtrate was evaporated to one third of the volume, and 10 mL
pentane was added to this causing a beige-colored solid material to
precipitate from the dark-brown solution. The suspension was
stirred for 20 minutes and then filtered. The solid material was
dried under a fine vacuum. 497 mg (54%) of a light-brown solid
material was obtained.
[0058] Note: Recrystallization from THP failed, although several
attempts were made.
[0059] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): .delta.=6.81-6.86
(m, 5H, H.sub.o, H.sub.2), 7.27-7.33 (m, 3H, H.sub.p, H.sub.4),
7.63-7.69 (m, 5H, H.sub.m, H.sub.3), 8.69 (d, 1 H,
.sup.3J.sub.HH=6.88 Hz, H.sub.5) ppm
[0060] No usable .sup.13C-NMR spectrum could be obtained.
[0061] .sup.31P-NMR (121.5 MHz, C.sub.6D.sub.6): .delta.=42.0 (d,
.sup.3J.sub.YP=9.18 Hz) ppm
[0062] Elemental analysis C.sub.54H.sub.42O.sub.3P.sub.3Y (920.74
g/mol); calculated: C, 70.44; H, 4.60; found: C, 67.22; H, 5.98
[0063] IR-spectroscopy (v/cm.sup.-1): 3024(w, br), 2936(w, br),
2844(w, br), 1483(w), 1435(m), 1194(w), 1131(w), 1118(m), 1080(m),
1063(w), 1047(w), 1025(w), 997(w), 871(w), 747(w), 720(m), 691(m),
627(w), 537(s), 460(m), 449(m)
[0064] Crystallographic data: trigonal, P 2.sub.1/a, a=14.4820(3)
.ANG., b=17.7836(4) .ANG., c=19.3122(4) .ANG., .alpha.=90.degree.,
.beta.=94.101(2).degree., .lamda.=90.degree., V=4960.97(18)
.ANG..sup.3, Z=4, D.sub.c=1.348 mg/m.sup.3, .mu.=1.320
mm'.sup.1,
[0065] F(000)=2088
EXAMPLE 3
[0066] [o-Lu(C.sub.5H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3]. 249
mg [LuCl.sub.3(thf).sub.3] (0.5 mmol) was weighed in together with
418 mg triphenylphosphine oxide (1.5 mmol) to which 10 mL THP was
added. The suspension was stirred for 30 min at RT, during which
time a coarse flaky solid material formed from the initially fine
crystalline material. The substance was then cooled to 0.degree. C.
and 0.75 mL PhLi solution (20% solution in Bu.sub.2O, 1.5 mmol) was
added, stirring was continued for two more hours at the given
temperature. The suspension increasingly turned to a brown color
during which time the majority of the solid material became
dissolved. The solvent was removed completely and the obtained
brown solid material was taken up in benzene, and then filtered
with Chelite.RTM.. The benzene was removed, and the product was
recrystallized from THP at -30.degree. C. After decanting, drying
occurred under a fine vacuum. 90 mg (18%) of a beige-brown-colored
solid material was obtained.
[0067] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): .delta.=6.81-6.87
(m, 5H, H.sub.0, H.sub.2), 7.30-7.35 (m, 3H, H.sub.p, H.sub.4),
7.65-7.71 (m, 5H, H.sub.m, H.sub.3), 8.61 (d, 1H,
.sup.3J.sub.HH=6.37 Hz, H.sub.5) ppm
[0068] "C-NMR (75.5 MHz, C.sub.6D.sub.6): .delta.=124.6 (d,
.sup.3J.sub.CP=14.5 Hz, C.sub.3), 128.3 (d, .sup.2J.sub.CP=11.5 Hz,
C.sub.o), 128.8 (s, C.sub.2), 129.2 (d, .sup.4J.sub.CP=4.2 Hz,
C.sub.4), 131.4 (d, .sup.4J.sub.CP=2.5 Hz, C.sub.p), 132.6 (d,
.sup.3J.sub.CP=10.4 Hz, C.sub.m), 133.7 (d, .sup.1J.sub.CP=97.9 Hz,
C.sub.ipso), 141.5 (d, .sup.3J.sub.CP=25.5 Hz, C.sub.5), 141.0 (d,
.sup.1J.sub.CP=119.2 Hz, C,), 206.9 (d, .sup.2J.sub.CP=40.4 Hz,
C.sub.Lu) ppm
[0069] [illegible]
[0070] Elemental analysis C.sub.54H.sub.42O.sub.3P.sub.3LU (1006.80
g/mol); calculated C, 64.42; H, 4.20; found: C, 63.77; H, 4.55
[0071] IR spectroscopy (v/cm.sup.-1): 3011(w, br), 1483(w),
1436(m), 1415(w), 1222(w), 1195(w), 1131(m), 1119(m), 1079(m),
1063(m), 1025(w), 998(w), 748(w), 721(m), 692(m), 628(w), 537(s),
463(m), 443(m), 414(m)
[0072] Crystallographic data: triclinic, P -1, a=11.4691(3) .ANG.,
b=14.3439(3) .ANG., c=19.7816(3) .ANG., .alpha.=93.949(2).degree.,
.beta.=90.486(2).degree., .gamma.=96.701(2).degree., V=3223.95(12)
.ANG..sup.3, Z=2, D.sub.c=1.392 mg/m.sup.3, .mu.=1.660 mm.sup.-1,
F(000)=1396
EXAMPLE 4
[0073] [o-Yb(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3]. 248
mg [YbCl.sub.3(thf).sub.3] (0.5 mmol) was weighed in together with
418 mg triphenylphosphine oxide (1.5 mmol) to which was added 10 mL
THP. The suspension was stirred for 30 min at RT, and during this
time a coarse flaky solid material formed from the initially fine
crystalline material. The substance was then cooled to 0.degree. C.
and 0.75 mL PhLi solution (20% solution in Bu.sub.2O, 1.5 mmol) was
added to this, and stirring was continued for two more hours at the
given temperature. The suspension increasingly turned a brown
color, wherein the majority of the solid material became dissolved
during this time. The solvent was removed completely, and the
obtained brown solid material was taken up in benzene and filtered
with Chelite.RTM.. The benzene was then removed, and the product
was recrystallized from THP at -30.degree. C. After decanting, the
substance was dried in a fine vacuum.
[0074] 126 mg (25%) of a beige-brown solid material was
obtained.
[0075] NMR spectroscopic analysis is not possible due to marked
paramagnetism.
[0076] Elemental analysis C.sub.54H.sub.42O.sub.3P.sub.3Yb (1004.87
g/mol); calculated C, 64.54; H, 4.21; found: C, 63.82; H, 4.62
[0077] IR spectroscopy (v/cm.sup.-1): 3025(w, br), 2926(w, br),
2844(w, br), 1483(w), 1435(m), 1194(w), 1131(w), 1117(m), 1082(m),
1063(w), 1047(w), 1025(w), 997(w), 871(w), 747(w), 720(m), 690(m),
627(w), 537(s), 460(m), 446(m)
EXAMPLE 5
[0078] Poly-.epsilon.-caprolactone. The polymerization of
.epsilon.-caprolactone always occurred at RT in toluene. Selected
catalyst/monomer ratio of 1:150
[0079] A solution of the needed catalyst quantity was prepared in
20 mL toluene to which was quickly added the corresponding quantity
of .epsilon.-caprolactone. Typically, an increase in viscosity was
quickly noticed. After a reaction time of one hour, the reaction
mixture in 200 mL was poured over methanol that had been cooled to
0.degree. C., and the polymer precipitated. The precipitate was
dried overnight at 40.degree. C. The sample preparation for the GPC
measurement included renewed dissolution in THF, followed by
filtration with a 0.45 .mu.m syringe filter and another
precipitation in 100 mL over methanol that cooled to 0.degree. C.
The polymer was filtered off again and dried at 40.degree. C. The
results of the experiments are compiled in Table 1.
TABLE-US-00001 TABLE 1 Summary of the polymerization results for
.epsilon.-caprolactone Chain length M.sub.w/ Catalyst Yield/g
Yield/% Polydispersity D g/mol Example 1 0.703 65 2.96 163260
Example 2 1.087 100 1.49 49733 Example 3 1.044 97 2.98 89342
[0080] Test for living polymerization. Using the example
[o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3], the goal was
to demonstrate that, in the case of the ring-opening polymerization
of .epsilon.-caprolactone with this substance class, there was in
fact a living polymerization. The chosen starting ratio of
catalyst/monomer was 1:150.
[0081] 46.4053 mg
[o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.3]. (0.0504 mmol)
was dissolved in 40 mL toluene and 0.8 mL .epsilon.-caprolactone
(7.5696 mmol) was added quickly at RT. After one hour, 10 mL of the
reaction mixture was removed and added in 200 mL on methanol that
had been cooled to 0.degree. C. The precipitated polymer was
filtered off and underwent a work-up. Another 10 mL toluene was
added to the remaining reaction mixture to reduce the viscosity.
Then, calculated for the catalyst quantity still remaining in the
reaction vessel, another 150 equivalents of E-caprolactone (0.6 mL,
5.6772 mmol) was added, and the substance was stirred for another
hour. This process was repeated twice. After each sample-taking,
the catalyst/monomer ratio was increased by 150 equivalents. The
results are compiled in Table 2.
TABLE-US-00002 TABLE 2 Result of the tests for living
polymerization Sample Yield/ Polydispersity Chain length monomer
Catalyst: mg Yield/% D M.sub.w/g/mol ratio Sample 1 56 26 1.20
15185 1:150 Sample 2 190 44 1.36 21892 1:300 Sample 3 318 45 1.45
23682 1:450 Sample 4 340 42 1.50 26700 1:600
[0082] Poly-L-lactide (A). Polymerization of L-lactide was always
done at room temperature in toluene. The ratio of catalyst/monomer
was selected as 1:150. The needed quantity of catalyst was
dissolved in 10 mL toluene and 3 mL of a solution of
(L,L)-dilactide in THP (c=0.99315 mol/L, 2.9795 mmol) was quickly
added. The substance was stirred for two hours at RT, then the
reaction mixture was poured over weak HCI-acidic methanol and the
polymer precipitated. The precipitate was dried overnight at
40.degree. C. The sample preparation for the GPC measurement was
done by dissolving the substance once more in THF, followed by
filtration with a 0.45 .mu.m syringe filter and another
precipitation in 100 mL on methanol that had been cooled to
0.degree. C. The polymer was filtered off again and dried at
40.degree. C. The results from the experiments are compiled in
Table 3.
TABLE-US-00003 TABLE 3 Summary of the polymerization results of
L-lactide Chain length Catalyst Yield/mg Yield/% Polydispersity D
M.sub.w Compound 317 73 -- 7212 4 244 57 1.49 10527 Compound 376 87
1.54
COMPARISON EXAMPLE 1
[0083] Poly-L-lactide (B). 40.000 mg
[o-Sn(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=O).sub.2] (0.05941
mmol, 1 eq) was dissolved in 5.0 mL toluene and added to a solution
of 2.569 g (L.L)-dilactide (0.01782 mmol, 300 eq) in 10.0 mL
toluene. The reaction mixture was heated for 24 hours to
100.degree. C. After cooling down, the reaction solution was poured
in 200 mL weak HCI-acidic methanol, and the polymer precipitated.
The precipitate was then dried overnight at 40.degree. C. To
prepare the sample for the GPC measurement, it was dissolved once
more in THF, followed by filtration with a 0.45 .mu.m syringe
filter and another precipitation in 100 mL on methanol cooled to
0.degree. C. The polymer was filtered off again and dried at
40.degree. C. 1.84 g poly-L-lactide (72%) was obtained.
[0084] GPC (THF (+TFA 5 vol %): D=1.45; 11/1,,=117180 g/mol.
EXAMPLE 6
[0085] Polyisoprene. 0.01 mmol of the precatalyst was provided in
7.8 mL chlorobenzene, and 1.0 mL isoprene (10 mmol) was added to
this. 8.012 mg [PhNHMe.sub.2][B(C.sub.6F.sub.5).sub.4] was then
added after having been dissolved in 1.0 mL chlorobenzene. After 15
minutes, 0.2 mL of a solution of TIBAL in toluene (c=0.0581 mol/L,
0.1164 mmol) was added, and the reaction mixture was stirred for 24
hours. To quench the polymerization, weakly HCl-acidic methanol was
used with a bit of 2,4-ditertbutyl-4-methyl-phenol. After
expiration of the reaction time, the weakly viscous reaction
solution was poured in 100 mL of the aforementioned methanolic
solution, which caused the polymer to precipitate. The precipitate
was then dried under a fine vacuum for ten hours. The sample
preparation for the GPC measurement was done by dissolving the
substance once again in 10 mL dichloromethane, followed by
filtration with a 0.45 .mu.m syringe filter and another
precipitation in 100 mL of the aforementioned methanolic solution.
The polymer was dried once more under a fine vacuum. The ratio of
the different possible coupling modes was established by a curve
analysis of the methyl proton signals. The signal for 1,2-coupled
polyisoprene was not observed. The .sup.1H-NMR spectra were
recorded in CDCl.sub.3. The results are compiled in Table 4.
TABLE-US-00004 TABLE 4 Summary of the polymerization results of
isoprene Polydisper- Chain Glass Coupling/ sity length point/ 1.4
cis: Catalyst Yield/mg Yield/% D M.sub.w .degree. C. 1.4 trans:
Expl 1 340 50 --* 63000* -62.1 92:2:6 Expl 2 650 96 1.69 44498
-62.2 75:6:19 *Regarding Example 1, a multimodal distribution was
determined by the GPC measurement. The polydispersity can therefore
not be established; M.sub.w was determined graphically from the
elugram of the measurement.
EXAMPLE 7
[0086] The synthesis of the homoleptic triphenylmethylidene
phosphorane complexes will be described below in an exemplary
manner for
[o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3]. The
syntheses as well as the growing of monocrystals in Examples 8 to
12 were done analogously.
[0087] [o-Y(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3].
206 mg [YCl.sub.3(thf).sub.3] (0.5 mmol) was weighed in together
with 414 mg (C.sub.6H.sub.5).sub.3P=CH.sub.2(1.5 mmol) and
dissolved in 10 mL THF. A yellow solution formed. After 15 minutes,
the reaction mixture was cooled down to 0.degree. C. and 0.75 mL
PhLi solution (20% ig in Bu.sub.2O, 1.5 mmol) was slowly dropped
in. After the completed addition, the reaction solution was slowly
heated to RT; in regular one-hour intervals, samples 0.5 mL each
were taken and tested via .sup.31P-NMR spectroscopy. The solution
increasingly turned an orange color, then a dark-brown. After six
hours, it was confirmed with .sup.31P-NMR spectroscopy that the
conversion was complete. The solvent was then removed in a fine
vacuum, and the residue was taken up in toluene, and then filtered
with Celite.RTM.. The filtrate was evaporated to half of the
volume, and 1 mL pentane was added. After the crystallization at
-30.degree. C., decanting and drying in a fine vacuum, it was
possible to isolate 288 mg (63%) of a yellow, fine-crystalline
solid material. By superimposing a saturated layer of a toluene
solution with pentane (ratio 1:1 (V:V)), it was possible to obtain
suitable monocrystals for the crystalline structural analysis.
[0088] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): .delta.=0.76 (dd,
2H, .sup.2J.sub.HH=9.35 Hz, .sup.2J.sub.HY=0.92 Hz, CH.sub.2), 6.85
-6.91 (m, 5H, H.sub.o, H.sub.2), 6.96-7.01 (m, 3H, H.sub.p,
H.sub.4), 7.32-7.38 (m, 5H, H.sub.m, H.sub.3), 8.71 (d, 1 H,
.sup.2J.sub.HH=6.59 Hz, H.sub.5) ppm
[0089] .sup.13C-NMR (75.5 MHz, C.sub.6D.sub.6): .delta.=14.1 (dd,
.sup.1J.sub.CP=41.1 Hz, .sup.1J.sub.CP=14.3 Hz, CH.sub.2), 124.2
(d, .sup.2J.sub.CP=13.0 Hz, Co), 130.4 (d, .sup.4J.sub.CP=2.6 Hz,
C.sub.r), 130.9 (d, .sup.4J.sub.CP=1.3 Hz, C.sub.4), 132.0 (d,
.sup.2J.sub.CP=9.5 Hz, C.sub.2), 132.6 (d, .sup.3J.sub.CP=9.6 Hz,
C.sub.3), 132.7 (d, .sup.3J.sub.CP=9.2 Hz, C.sub.m), 134.3 (d,
.sup.1J.sub.CP=69.8 Hz, C.sub.ipso), 139.1 (dd,
.sup.1J.sub.CP=112.6, .sup.2J.sub.CP=2.0 Hz, C.sub.1), 140.3 (d,
.sup.3J.sub.CP=27.8 Hz, C.sub.5), 204.1 (dd, .sup.2J.sub.CP=52.8
Hz, .sup.1J.sub.CP=33.4 Hz, C.sub.y) ppm
[0090] .sup.31P-NMR (121.5 MHz, C.sub.6D.sub.6): .delta.=26.7 (d,
.sup.2J.sub.PT=4.0 Hz) ppm
[0091] Elemental analysis C.sub.57H.sub.48P.sub.3Y (914.82 g/mol);
calculated C, 74.84; H, 5.29; found: C, 73.19; H, 5.50
[0092] IR spectroscopy (v/cm.sup.-1): 2970(w, br), 1433(m),
1413(w), 1102(m), 1070(m), 998(w), 868(m), 741 (m), 720(m), 690(m),
665(m), 625(m), 520(s), 491 (m), 455(m), 433(w), 404(w)
[0093] Crystallographic data: trigonal, R-3, a=20.085(5) .ANG.,
b=20.085(5) .ANG., c=20.610(5) .ANG., a=13=90.000(5).degree.,
.lamda.=120.000(5).degree., V=8947(4) .ANG..sup.3, Z=6,
D.sub.c=1.358 mg/m.sup.3, .mu.=1.450 mm.sup.-1, F(000)=3792
EXAMPLE 8
[0094]
[o-Sc(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3]. The
synthesis followed a 0.5 mmol scale. The reaction time was 24
hours. Following recrystallization, 322 mg (74%) of a yellow,
fine-crystalline solid material was obtained.
[0095] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): .delta.=1.01 (d,
2H, .sup.2J.sub.HH=9.58 Hz, CH.sub.2), 6.90-7.05 (m, 5H, Ho,
H.sub.2), 7.29-7.35 (m, 3H, H.sub.p, H.sub.4), 7.61-7.66 (m, 5H,
H.sub.m, H.sub.3), 8.41 (d, 1H, .sup.2J.sub.HH=6.76 Hz, H.sub.5)
ppm
[0096] .sup.13C-NMR (75.5 MHz, C.sub.6D.sub.6): 12.8 (d,
.sup.1J.sub.CP=39.2 Hz, CH.sub.2), 124.1 (d, .sup.2J.sub.CP=12.9
Hz, Co), 128.4 (d, .sup.3J.sub.CP=11.4 Hz, C.sub.2), 130.4 (d,
.sup.4J.sub.CP=2.3 Hz, C.sub.p), 130.6 (d, .sup.4J.sub.CP=2.4 Hz,
C.sub.4), (d, .sup.2J.sub.CP=9.7 Hz, C.sub.m), 132.7 (d,
.sup.3J.sub.CP=9.0 Hz, C.sub.3), 134.3 (d, .sup.1J.sub.CP=69.2 Hz,
C.sub.ipso), 137.7 (d,
[0097] .sup.1J.sub.CP32 113.2 Hz, C,), 140.7 (d,
.sup.3J.sub.CP=27.3 Hz, C.sub.5), (C.sub.Sc would not be observed)
ppm
[0098] .sup.31P-NMR (121.5 MHz, C.sub.6D.sub.6): .delta.=31.1 (s)
ppm
[0099] Elemental analysis C.sub.57H.sub.48P.sub.3Sc (870.87 g/mol);
calculated: C, 78.61; H, 5.56; found: C, 78.68; H, 6.05
[0100] IR spectroscopy (v/cm.sup.-1): 3020(w, br), 2946(w, br),
1480(w), 1434(m), 1414(w), 1102(m), 1073(m), 1027(w), 998(w),
970(w), 931(w), 868(m), 749(m), 737(s), 711(m), 691(s), 630(m),
532(m), 513(s), 452(s), 434(m), 412(m)
[0101] Crystallographic data: trigonal, R-3, a=19.9558(15) .ANG.,
b=19.9558(15) .ANG., c=25.421(2) .ANG., .alpha.=.beta.=90.degree.,
.gamma.=120.degree., V=8767(12) .ANG..sup.3, Z=6, D.sub.c=1.094
mg/m.sup.3, .mu.=0.244 mm.sup.-1, F(000)=3036
EXAMPLE 9
[0102]
[o-Lu(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3]. The
synthesis followed a 0.5 mmol scale. The reaction time was 24
hours. Following recrystallization, 345 mg (69%) of the yellow
crystalline product was obtained.
[0103] .sup.1H-NMR (300.1 MHz, C.sub.5D.sub.6): .delta.=0.73 (d,
1H, .sup.2J.sub.HH=9.61 Hz, CH.sub.2), 6.87-6.92 (m, 5H, H.sub.0,
H.sub.2), 6.98-7.07 (m, 3H, H.sub.p, H.sub.4), 7.28-7.34 (m, 5H,
H.sub.m, H.sub.3), 8.66 (d, 1H, .sup.3J.sub.HH=6.79 Hz, H.sub.5)
ppm
[0104] .sup.13C-NMR (75.5 MHz, C.sub.6D.sub.6): .delta.=17.2 (d,
.sup.1J.sub.CP=40.0 Hz, CH.sub.2), 124.1 (d, .sup.2J.sub.CP=13.1
Hz, Co), 130.4 (d, .sup.4J.sub.CP=2.5 Hz, C.sub.p), 130.5 (d,
.sup.4J.sub.CP=2.8 Hz, C.sub.4), 132.6 (d, .sup.2J.sub.CP=6.0 Hz,
C.sub.2), 132.7 (d, .sup.3J.sub.CP=5.6 Hz, C.sub.3), 134.4 (d,
.sup.3J.sub.CP=12.2 Hz, C.sub.m), 134.7 (d, .sup.1J.sub.CP=69.9 Hz,
C.sub.ipso), 139.5 (d, .sup.1J.sub.CP=112.1 Hz, C.sub.1), 141.2 (d,
.sup.3J.sub.CP=27.6 Hz, C.sub.5), 211.5 (d, .sup.2J.sub.CP=52.7 Hz,
Cu) ppm
[0105] .sup.31P-NMR (121.5 MHz, C.sub.6D.sub.6): .delta.=29.6 (s)
ppm
[0106] Elemental analysis C.sub.57H.sub.48P.sub.3Lu (1000.88
g/mol); calculated: C, 66.40; H, 4.83; found: C, 66.44; H, 5.50
[0107] IR spectroscopy (v/cm.sup.-1): 3011(w, br), 2949(w, br),
1434(m), 1412(w), 1174(w), 1113(w), 1099(m), 1070(m), 1027(w),
998(w), 979(w), 927(m), 868(m), 730(m), 712(m), 691 (s), 627(w),
558(w), 512(s, br), 464(m), 447(m), 408(m)
[0108] Crystallographic data: trigonal, R-3, a=20.0214(8) .ANG.,
b=20.0214(8) .ANG., c=25.5605(13) .ANG., .alpha.=.beta.=90.degree.,
.gamma.=120.degree., V=8873.4(7) .ANG..sup.3, Z=6, D.sub.c=1.124
mg/m.sup.3, p=1.779 mm.sup.-1, F(000)=3036
EXAMPLE 10
[0109]
[o-Dy(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2).sub.3]. The
synthesis followed a 0.5 mmol scale. The reaction time was 6 hours.
Following recrystallization, 351 mg (71%) of the desired product
were isolated.
[0110] Elemental analysis C.sub.57H.sub.48P.sub.3Dy (988.41 g/mol);
calculated: C, 69.26; H, 4.98; found: C, 69.63; H, 5.25.
[0111] IR spectroscopy (v/cm.sup.-1): 2947(w, br), 1433(m),
1102(w), 1069(w), 1026(w), 997(w), 921 (w), 871 (w), 742(w),
716(m), 691 (s), 625(w), 521 (s), 492(m), 456(w), 439(w),
404(w)
[0112] Crystallographic data: triclinic, P-1, a=10.4014(4) .ANG.,
b=16.8153(7) .ANG., c=18.5046(7) .ANG., .alpha.=113.568(3).degree.,
.beta.=99.621 (3).degree., .gamma.=92.223(3).degree., V=2904.8(2)
.ANG..sup.3, Z=2, D.sub.c=1.281 mg/m.sup.3, p=1.407 mm.sup.-1,
F(000)=1145
EXAMPLE 11
[0113] [o-Gd(C.sub.6H.sub.4(C.sub.6H.sub.5).sub.2P=CH.sub.2)]. The
synthesis followed a 0.5 mmol scale. The reaction time was six
hours. Following recrystallization, 275 mg (56%) of the yellow
crystalline target compound was obtained.
[0114] Elemental analysis C.sub.57H.sub.48P.sub.3Gd (983.16 g/mol);
calculated: C, 69.63; H, 4.92; found: C, 60.14; H, 4.63
[0115] IR spectroscopy (v/cm.sup.4): 2968(w, br), 1433(m), 1413(w),
1102(m), 1068(m), 1026(w), 997(w), 913(w), 872(m), 741 (m), 720(m),
690(s), 624(m), 519(s), 489(s), 455(m), 437(m)
[0116] Crystallographic data triclinic, P-1, a=10.4014(4) .ANG.,
b=16.8153(7) .ANG., c=18.5046(7) .ANG., .alpha.=13.568(3).degree.,
.beta.=99.621 (3).degree., .gamma.=92.223(3).degree., V=2904.8(2)
.ANG..sup.3, Z=2, D.sub.c=1.282 mg/m.sup.3, .mu.=1.263 mm.sup.-1,
F(000)=1148
EXAMPLE 12
[0117] [o-Sm(C.sub.6H4(C.sub.6H5)2P=CH2)3] The synthesis followed a
0.5 mmol scale. The reaction time was 3 hours. Following
recrystallization, 376 mg (77%) of the compound 13 was
isolated.
[0118] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): .delta.=1.11 (d,
2H, .sup.2J.sub.HH=7.68 Hz, CH.sub.2), 6.55-6.60 (m, 4H, H.sub.o),
6.69-6.82 (m, 7H, H.sub.m, H.sub.p), 7.01-7.05 (m, 1H, H.sub.3),
7.71-7.77 (m, 1H, H.sub.4), 8.01-8.05 (m, 1H, H.sub.2), 12.46 (d,
1H, .sup.3J.sub.HH=6.25 Hz, H.sub.5) ppm
[0119] .sup.13C-NMR (75.5 MHz, C.sub.6D.sub.6): .delta.=-4.3 (d,
.sup.2J.sub.CP=100.2 Hz, CH.sub.2), 124.2 (d, .sup.2J.sub.CP=13.0
Hz, C.sub.2), 128.5 (d, .sup.3J.sub.CP=17.2 Hz, C.sub.o), 130.4 (d,
.sup.4J.sub.CP=2.5 Hz, C.sub.p), 130.6 (d, .sup.4J.sub.CP=2.7 Hz,
C.sub.4), 132.6 (d, .sup.2J.sub.CP=9.5 Hz, C.sub.o), 132.7 (d,
.sup.3J.sub.CP=8.4 Hz, C.sub.m), 134.3 (d, .sup.1J.sub.CP=69.5 Hz,
C.sub.ipso), 139.1 (d, .sup.1J.sub.CP=112.6 Hz, C.sub.1), 140.3 (d,
.sup.3J.sub.CP=27.9 Hz, C.sub.5), 204.1 (d, .sup.2J.sub.CP=52.6 Hz,
C.sub.sm) ppm
[0120] .sup.31P-NMR (121.5 MHz, C.sub.6D.sub.6): .delta.=24.0 (s,
br) ppm
[0121] Elemental analysis C.sub.57H.sub.45P.sub.3Sm (976.27 g/mol);
calculated: C, 70.12; H, 4.96; found: C, 69.90; H, 4.87
[0122] IR spectroscopy (v/cm.sup.-1): 2969(w, br), 1433(m),
1130(w), 1103(m), 1069(w), 1026(w), 997(w), 872(m), 741(m), 721(m),
691(s), 656(m), 624(m), 517(s), 490(s), 454(m), 431(m), 414(m)
[0123] Crystallographic data: triclinic, P-7, a=10.4202(5) .ANG.,
b=16.8904(8) .ANG., c=18.5499(9) .ANG., .alpha.=113.512(4).degree.,
.beta.=99.832(4).degree., .gamma.=92.138(4).degree., V=2929.6(2)
.ANG..sup.3, Z=2, D.sub.c=1.316 mg/m.sup.3, .mu.=1.125 mm".sup.1,
F(000)=1194
EXAMPLE 13
[0124] Poly-.epsilon.-caprolactone. The polymerization of
.epsilon.-caprolactone always occurred at RT in toluene. The
catalyst/monomer ratio was selected as 1:500.
[0125] A solution of the needed quantity of catalyst was prepared
in 20 mL toluene to which was quickly added the corresponding
quantity of .epsilon.-caprolactone. Typically, it was possible to
observe a very rapid increase in viscosity. After an hour of
reaction time, the reaction mixture was poured in 200 mL on
methanol that had been cooled to auf 0.degree. C. causing the
polymer to precipitate. Said precipitate dried overnight at
40.degree. C. The sample preparation for the GPC measurement was
done by a further dissolution in THF, followed by filtration with a
0.45 .mu.m syringe filter and another precipitation in 100 mL on
methanol cooled to 0.degree. C. The polymer was filtered off again
and dried at 40.degree. C. The results of the experiments are
compiled in Table 5.
TABLE-US-00005 TABLE 5 Summary of the polymerization results of
.epsilon.-caprolactone Polydispersity Chain length Catalyst Yield/g
Yield/% D M.sub.w Exp. 7 1.766 75 2.54 45117 Exp. 8 2.330 82 1.74
47713
EXAMPLE 14
[0126] Polyisoprene. 0.01 mmol of the precatalyst was provided in
7.8 mL chlorobenzene and 1.0 mL isoprene (10 mmol) was added to
this. After this, 8.012 mg [PhNHMe.sub.2][B(C.sub.6F.sub.5).sub.4]
was added, after it had been dissolved in 1.0 mL chlorobenzene.
After 15 minutes, 0.2 mL of a solution of TIBAL in toluene
(c=0.0581 mol/L, 0.1164 mmol) was added, and the reaction mixture
was stirred for 24 hours. Weak HCl-acidic methanol with some
2,4-ditertbutyl-4-methyl-phenol was used to quench the
polymerization. After the expiration of the reaction time, the
weakly viscous reaction solution was poured in 100 mL of the
aforementioned methanolic solution causing the precipitation of the
polymer. The same was dried in a fine vacuum for ten hours. The
sample preparation for [text missing] was done with a 0.45 .mu.m
syringe filter, and again precipitation in 100 mL of the
aforementioned methanolic solution. The precipitate was once again
dried in a fine vacuum. The ratio of the different possible
coupling modes was determined by a curve analysis of the methyl
proton signals. The signal for 1,2-coupled polyisoprene was not
observed. The .sup.1H-NMR spectra were recorded in CDCl.sub.3. The
results of the experiments are compiled in Table 6.
TABLE-US-00006 TABLE 6 Summary of the polymerization results of
isoprene Polydisper- Chain Glass Coupling/ Yield/ Yield/ sity
length point/ 1,4-cis: Catalyst mg % D M.sub.w/g/mol .degree. C.
1,4-trans: Exp. 7 680 100 1.60 55582 -55.4 70:14:16 Exp. 8 260 38 *
58000* -56.3 76:11:14 *Regarding Example 8, the GPC measurement
revealed a multimodal distribution. The polydispersity can
therefore not be determined; M.sub.w was graphically established
from the elugram of the measurement.
* * * * *